Fibre-reactive anthraquinone dyes, process for their preparation and the use thereof

ABSTRACT

Anthraquinone dyes of formula  
                 
wherein 
     R 1 , R 2  and R 3  are each independently of one another hydrogen or unsubstituted or substituted C 1 -C 12 alkyl,    X 1  is chloro or fluoro,    B 1  is methylene-phenylene-methylene which is unsubstituted or substituted in the phenylene ring by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 2 -C 4 alkanoylamino, halogen, carboxy or sulfo, or is a radical of formula —(CH 2 ) 3 —CH(CH 3 )—CH 2 —, —CH 2 —CH 2 —CH(C 2 H 5 )—, —CH 2 —CH(OH)—CH 2 — or —CH 2 —C(CH 3 ) 2 —CH 2 —,    Y is hydrogen, unsubstituted or substituted C 1 -C 12 alkyl, or phenyl or naphthyl, each unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 2 -C 4 alkanoylamino, halogen, carboxy, sulfo or a radical of formula —SO 2 -Z, wherein    Z is a group of formula —CH═CH 2  or —CH 2 —CH 2 —U 1 , and U 1  is a leaving group, are particularly suitable for dyeing or printing cellulosic fibre materials or natural or synthetic polyamide fibre materials in high tinctorial yield and give dyeings and prints of good fastness properties.

The present invention relates to novel fibre-reactive anthraquinonedyes, to a process for their preparation and to the use thereof fordyeing or printing fibre materials.

The practice of dyeing with reactive dyes in recent years has led tomore exacting demands being made of the quality of the dyeings obtainedand to the efficiency of the dyeing process. Consequently there is acontinuing need to provide novel reactive dyes that have enhancedproperties, especially with respect to application.

At the present time it is required of reactive dyes that they shall havesufficient substantivity for the substrate to be dyed and at the sametime have the property that unfixed dye is easily washed off. They arefurther required to afford a good tinctorial yield and have highreactivity to give in particular dyeings of good fixation. The knowndyes do not meet these requirements in all respects.

It is therefore the object of this invention to provide novel, improvedreactive dyes for dyeing and printing fibre materials that have thequalities referred to above to a high degree. The novel dyes shall inparticular be distinguished by high fixation yields and high fibre-dyebonding stability, and it shall furthermore be possible to wash-offunfixed dye on the fibre with ease. The novel dyes shall also producedyeings with good allround fastness properties, preferably light- andwetfastness properties.

It has been found that the novel reactive dyes defined hereinaftersubstantially meet these requirements.

Accordingly, the invention relates to anthraquinone dyes of formula

whereinR₁, R₂ and R₃ are each independently of one another hydrogen orunsubstituted or substituted C₁-C₁₂alkyl,X₁ is chloro or fluoro,B₁ is methylene-phenylene-methylene which is unsubstituted orsubstituted in the phenylene ring by C₁-C₄alkyl, C₁-C₄alkoxy,C₂-C₄alkanoylamino, halogen, carboxy or sulfo, or is a radical offormula —(CH₂)₃—CH(CH₃)—CH₂—, —CH₂—CH₂—CH(C₂H₅)—, —CH₂—CH(OH)—CH₂— or—CH₂—C(CH₃)₂—CH₂—,Y is hydrogen, unsubstituted or substituted C₁-C₁₂alkyl, or phenyl ornaphthyl, each unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy,C₂-C₄alkanoylamino, halogen, carboxy, sulfo or a radical of formula—SO₂-Z, whereinZ is a group of formula —CH═CH₂ or —CH₂—CH₂—U₁, and U₁ is a leavinggroup.

Suitable C₁-C₁₂alkyl radicals R₁, R₂, R₃ and Y are preferablyC₁-C₁₀alkyl radicals, more particularly C₁-C₈alkyl radicals. These alkylradicals, with the exception of methyl, may be interrupted by oxygen,preferably by 1, 2 or 3 members —O—, more particularly by 1 or 2 members—O—. These alkyl radicals may be also be unsubstituted or substituted,possible substituents being hydroxyl, sulfo or sulfato, preferablyhydroxyl or sulfo, most preferably hydroxyl. The substituent Y definedas alkyl may further be substituted by the radical of an anthraquinonedye, typically by a radical of 1,4-diaminoanthraquinone-2-sulfonic acid,which is bonded through the amino group in 4-position.

The radical B₁ in the significance of methylene-phenylene-methylene maybe unsubstituted or substituted in the phenylene ring by C₁-C₄alkyl,typically methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butylor isobutyl, preferably methyl, or by C₁-C₄alkoxy, typically methoxy,ethoxy, propoxy, isopropoxy, butoxy or isobutoxy, preferably methoxy, byC₂-C₄alkanoylamino such as acetylamino or propionylamino, by halogensuch as fluoro, chloro or bromo, preferably chloro, or by sulfo orcarboxy. The methylene-phenylene-methylene radical is preferablyunsubstituted or substituted in the phenylene ring by C₁-C₄alkyl,C₁-C₄alkoxy, halogen or sulfo. The corresponding unsubstituted radicalsare of particular interest.

The phenyl and naphthyl radicals represented by Y may be unsubstitutedor substituted by C₁-C₄alkyl, typically methyl, ethyl, propyl,isopropyl, butyl, sec-butyl, tert-butyl or isobutyl, preferably methyl,or by C₁-C₄alkoxy, typically methoxy, ethoxy, propoxy, isopropoxy,butoxy or isobutoxy, preferably methoxy, or by C₂-C₄alkanoylamino suchas acetylamino or propionylamino, by halogen such as fluoro, chloro orbromo, preferably chloro, or by sulfo, carboxy or by a radical offormula —SO₂-Z.

Suitable leaving groups U₁ are typically —Cl, —Br, —F, —OSO₃H, —SSO₃H,—OCO—CH₃, —OPO₃H₂, —OCO—CCl₃, —OCO—CHCl₂, —OCO—CH₂Cl, —OSO₂—C₁-C₄alkyl,—OSO₂—N(C₁-C₄alkyl)₂ or —OCO—C₆H₅.

Preferably U₁ is a group of formula —Cl, —OSO₃H, —SSO₃H, —OCO—CH₃,—OCO—C₆H₅ or —OPO₃H₂, preferably —Cl or —OSO₃H, preferably —OSO₃H.

R₁ and R₂ are preferably hydrogen or C₁-C₄alkyl, more particularlyhydrogen.

R₃ is preferably hydrogen or C₁-C₈alkyl which is unsubstituted orsubstituted by hydroxyl, sulfo or sulfato and, with the exception ofmethyl, may be interrupted by oxygen, and is more particularly hydrogenor unsubstituted or hydroxyl-substituted C₁-C₄alkyl. The most preferredmeaning is hydrogen.

R₁ and R₂ are more particularly hydrogen or C₁-C₄alkyl, most preferablyhydrogen, and R₃ is hydrogen or C₁-C₈alkyl which is unsubstituted orsubstituted by hydroxyl, sulfo or sulfato and, with the exception ofmethyl, may be interrupted by oxygen. More particularly R₃ is hydrogenor unsubstituted or hydroxyl-substituted C₁-C₄alkyl, and is mostpreferably hydrogen.

R₁, R₂ and R₃ are most preferably hydrogen.

B₁ in the significance of methylene-phenylene-methylene is preferably aradical of formula

wherein R₄ and R₅ are each independently of the other hydrogen,C₁-C₄alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylamino, halogen, carboxy or sulfo,preferably hydrogen, C₁-C₄alkyl, C₁-C₄alkoxy, halogen or sulfo and, mostpreferably, hydrogen.

Suitable alkylene linking groups B₁ mentioned above are preferably thoseof formula —(CH₂)₃—CH(CH₃)—CH₂—, —CH₂—CH(OH)—CH₂— or —CH₂—C(CH₃)₂—CH₂—,more particularly those of formula —(CH₂)₃—CH(CH₃)—CH₂— or—CH₂—C(CH₃)₂—CH₂—. The radical of formula —CH₂—C(CH₃)₂—CH₂— isparticularly preferred.

Preferably B₁ is a methylene-phenylene-methylene radical which isunsubstituted or substituted as indicated above or a radical of formula—(CH₂)₃—CH(CH₃)—CH₂— or, preferably, —CH₂—C(CH₃)₂—CH₂—, saidmethylene-phenylene-methylene radical having the meanings and preferredmeanings cited above.

More particularly, B₁ is methylene-phenylene-methylene or a radical offormula —CH₂—C(CH₃)₂—CH₂—.

Most preferably, B₁ is a radical of formula —CH₂—C(CH₃)₂—CH₂—.

Y is preferably hydrogen; C₁-C₁₂alkyl which is unsubstituted orsubstituted hydroxyl, sulfo or sulfato and, with the exception ofmethyl, interrupted by oxygen; or phenyl or naphthyl, each unsubstitutedor substituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylamino, halogen,carboxy, sulfo or a radical of formula —SO₂-Z, wherein Z is a group offormula —CH═CH₂ or —CH₂—CH₂—U₁, and U₁ is preferably chloro or sulfato;or an anthraquinone radical of formula

wherein B₂ is C₂-C₁₂alkylene which is unsubstituted or substituted byhydroxyl, sulfo or sulfato, and which may be interrupted by oxygen, ormethylene-phenylene-methylene which is unsubstituted or substituted inthe phenylene ring by C₁-C₄alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylamino,halogen, carboxy or sulfo.

The radicals B₂ preferably have the meanings and preferred meaningscited above for B₁. Particularly preferred substituents Y are theabove-mentioned phenyl and naphthyl radicals.

More particularly, Y is phenyl or naphthyl which are each unsubstitutedor substituted by C₁-C₄alkyl, C₁-C₄alkoxy, halogen, sulfo or a radicalof formula —SO₂-Z, wherein Z is preferably a group of formula —CH═CH₂ or—CH₂—CH₂—U₁, and U₁ is chloro or sulfato.

Most preferably, Y is sulfo-substituted naphthyl or, more particularly,phenyl which is substituted by C₁-C₄alkyl, C₁-C₄alkoxy, halogen, sulfoor a radical of formula —SO₂-Z, preferably by sulfo. Z is herepreferably a group of formula —CH═CH₂ or —CH₂—CH₂—U₁, and U₁ is chloroor sulfato.

Preferred anthraquinone dyes of formula (1) are those of formulae

wherein R₆, R₇ and R₈ are each independently of one another hydrogen,C₁-C₄alkyl, C₁-C₄alkoxy, halogen, sulfo or a radical of formula —SO₂-Z,wherein Z has the meanings and preferred meanings and preferred meaningscited above. Preferably Z is a group of formula —CH═CH₂ or —CH₂—CH₂—U₁,wherein U₁ is chloro or sulfato.

A further group of preferred anthraquinone dyes of formula (1) comprisesthe dyes of formulae

wherein R₉, R₁₀ and R₁₁ are each independently of one another hydrogen,C₁-C₄alkyl, C₁-C₄alkoxy, halogen, sulfo or a radical of formula —SO₂-Z,wherein Z has the meanings and preferred meanings cited above.Preferably Z is a group of formula —CH═CH₂ or —CH₂—CH₂—U₁, wherein U₁ ischloro or sulfato.

R₆, R₇, R₈, R₉, R₁₀ and R₁₁ are preferably each independently of oneanother hydrogen or sulfo. Most preferably, R₆, R₇, R₉ and R₁₀ are sulfoand R₈ and R₁₁ are hydrogen.

The dyes of formulae (5) and (7) are of particular interest, especiallythe dye of formula (5), wherein R₆, R₇, R₈, R₉, R₁₀ and R₁₁ have themeanings and preferred meanings cited above.

The invention further relates to a process for the preparation ofanthraquinone dyes of formula (1), which comprises condensing ananthraquinone dye of formula

with a compound of formula

and subsequently carrying out an optional conversion reaction, in whichformulae X₂ is chloro or fluoro and R₁, R₂, R₃, X₁, B₁ and Y have themeanings and preferred meanings given above.

The conversion reaction carried out after the synthesis may be anelimination reaction. For example, the anthraquinone dyes of formula (1)which contain sulfatoethylsulfonyl radicals may be treated with a base,conveniently sodium hydroxide, such that the sulfatoethylsulfonylradicals are converted into vinylsulfonyl radicals.

In principle, the anthraquinone dyes of formula (1) may be prepared bystarting from precursors or intermediates of dyes that containfibre-reactive radicals, or introducing said fibre-reactive radicalsinto intermediates of dye character suitable for this purpose.

The compounds of formulae (8) and (9) are known or can be obtained inanalogy to known processes.

The individual condensation reactions will usually be carried out in perse known manner in aqueous solution and in the temperature range from 0to 50° C., preferably from 0 to 10° C., and in the pH range fromtypically 4 to 10.

The novel dyes of formula (1) are obtained either in the form of thefree acid or, preferably, of salts thereof. Suitable salts are typicallythe alkali metal salts, alkaline earth metal salts or ammonium salts orthe salts of an organic amine. Illustrative examples are the sodium,lithium, potassium or ammonium salts or the salt of mono-, di- ortriethanolamine.

The novel dyes are suitable for dyeing and printing a wide range ofmaterials such as hydroxyl-group containing or nitrogen-containing fibrematerials. Such materials are typically silk, leather, wool, polyamidesand polyurethanes, and preferably cellulosic fibre materials of allkinds. Such cellulosic materials typically include the natural cellulosefibres such as cotton, linen and hemp, as well as cellulose andregenerated cellulose. The novel dyes are also suitable for dyeing orprinting hydroxyl-group containing fibres which are components ofblended fabrics, suitably cotton/polyester or cotton/polyamide blends.The novel dyes are particularly suitable for dyeing or printingcellulosic fibre materials. In addition, they may be used for dyeing orprinting natural or synthetic polyamide fibre materials, preferably woolor synthetic polyamide fibre materials.

The dyes of this invention can be applied to the fibre material by awide variety of means, preferably in the form of aqueous dye solutionsand print pastes. They are suitable for dyeing by the exhaust process aswell as by the pad process, in which the goods are impregnated withaqueous dye solutions which may or may not contain salt, and the dyesare fixed after treatment with alkali or in the presence of alkali, withor without the application of heat. The novel anthraquinone dyes arealso suitable for the cold pad-batch process, in which the dye isapplied together with the alkali on the pad and subsequently fixed bystoring the fabric for several hours at room temperature. Afterfixation, the dyeings or prints are washed thoroughly with cold and hotwater, with or without the addition of an agent that acts as adispersant and promotes the diffusion of unfixed dye.

The dyes of this invention are distinguished by high reactivity, goodfixation and very good build-up. They can therefore be used by theexhaust dyeing process at low dyeing temperatures, and require onlyshort steaming times in the pad-steam process. Fixation is high andunfixed dye can be easily washed off, the difference between degree ofexhaustion and degree of fixation being notably small, i.e the soap lossis minimal. The novel dyes are also particularly suitable for printing,especially on cotton, and likewise for printing nitrogen-containingfibres, typically silk, or also fibre blends that contain wool or silk.

The dyeings and prints obtained with the dyes of this invention havesuperior tinctorial strength and excellent fibre-dye bonding stabilityin the acid as well as in the alkaline range. They also have goodlightfastness and very good wetfastness properties, including fastnessto washing, water, seawater, crossdyeing and perspiration, as well asgood fastness to pleating, ironing and rubbing.

The invention is illustrated by the following Examples in which partsand percentages, unless otherwise indicated, are by weight. Therelationship between parts by weight and parts by volume is the same asthat between the kilogram and the litre.

EXAMPLE 1

19 parts of cyanuric chloride are stirred vigorously into 50 parts ofwater at 0° C., while adding a wetting agent and 5 parts of disodiumhydrogenphosphate. A neutral solution of 17 parts of2-aminobenzenesulfonic acid in 170 parts of water is then added dropwiseto this mixture, while keeping the pH constant at 4.5 by the addition ofsodium hydroxide solution. When the reaction is complete, a solution of38 parts of the anthraquinone compound of formula

dissolved with 4 parts of lithium hydroxyde monohydrate in 380 parts ofwater, are added dropwise such that the pH does not exceed 10. The pH isthen kept at 9.5 until completion of the reaction. The dye is salted outby addition of sodium chloride, isolated by filtration, washed with anaqueous solution of sodium chloride and dried, giving a dye of formula

in the form of the free acid. The dye of formula (102) dyes cotton andwool in a blue shade.

EXAMPLES 2-81

The procedure of Example 1 is repeated, but replacing 17 parts of2-aminobenzenesulfonic acid with an equimolar amount of an amine offormula H—V₁, and 38 parts of an anthraquinone of formula (101) with anequimolar amount of an anthraquinone of formula

giving the dyes listed in the following Table 1 of general formula

wherein B₁ and V₁ each have the meanings given in Table 1. The dyeslisted in Table 1 dye cotton and wool in blue shades. TABLE 1 Ex. V₁ B₁2

3

4

5

6

7

8

9

10

11

12

13

14

15

16

17

18

19

20

21 —NH—CH₂CH₂—SO₃H

22

23

24

25

26

27

28

29

30

31

32

33

34

35

36

37

38

39

40

41

42

43

44

45 —NH—CH₂CH₂—SO₃H

46

47

48

49

50

51

52

53

54

55

56

57

58

59

60

61

62

63

64

65

66

67

68

69 —NH—CH₂CH₂—SO₃H

70

71

72

73

74

75

76

77

78

79 —NH—CH₂CH₂—SO₃H

80

81

EXAMPLE 82

13 parts of cyanuric chloride are added dropwise to a solution of 17parts of 2-aminobenzenesulfonic acid in 150 parts of water neutralisedwith sodium hydroxide and buffered with 5 parts of disodiumhydrogenphosphate, while keeping the pH constant at 7 by the addition ofsodium hydroxide solution. When the reaction is complete, a solution of38 parts of an anthraquinone of formula

dissolved with 4 parts of lithium hydroxyde monohydrate in 380 parts ofwater, are added dropwise such that the pH does not exceed 10. The pH isthen kept at 9.5 until completion of the reaction. The dye is salted outby addition of sodium chloride, isolated by filtration, washed with anaqueous solution of sodium chloride and dried, giving a dye of formula

in the form of the free acid. The dye of formula (105) dyes cotton andwool in a blue shade.

The procedure of this Example is repeated, but replacing 17 parts of2-aminobenzenesulfonic acid with an equimolar amount of an amine offormula H—V₁, and 38 parts of an anthraquinone of formula (101) with anequimolar amount of an anthraquinone of formula

wherein B₁ and V₁ each have the meanings given in Examples 2-81, givingdyes of the general formula

wherein B₁ and V₁ each have the meanings given in Examples 2-81, andwhich dye cotton and wool in blue shades.

In the Examples in which a product containing a β-sulfatoethylsulfonylgroup is reacted with an anthraquinone, said reaction is carried out inmore dilute medium at a pH of c.8.5.

Dyeing Instruction

2 parts of the reactive dye obtained in Example 1 are dissolved in 400parts of water. To this solution are added 1500 parts of a solutionwhich contains 53 g/l of sodium chloride. Then 100 parts of cottonfabric are put into this dyebath at 40° C., followed by the additionafter 45 minutes of a solution containing 16 g/l of sodium hydroxide and20 g/l of anhydrous Na₂CO₃. The temperature of the dyebath is kept at40° C. for a further 45 minutes. The dyed goods are then rinsed, soapedat the boil for ¼ hour with a nonionic detergent, rinsed once more anddried.

Printing Instruction

With rapid stirring, 3 parts of the dye obtained in Example 1 arestrewed into 100 parts of a stock thickening which contains 50 parts of5% sodium alginate thickener, 27.8 parts of water, 20 parts of urea, 1part of sodium m-nitrobenzenesulfonate and 1.2 parts of sodiumhydrogencarbonate. A cotton fabric is printed with the resultantprinting paste and dried. The printed fabric is then steamed for 2minutes at 102° C. in saturated steam. The printed fabric is thenrinsed, if necessary soaped at the boil, rinsed once more and dried.

1-15. (canceled)
 16. An anthraquinone dye of the formula

wherein R₁, R₂ and R₃ are each independently of one another hydrogen orC₁-C₁₂ alkyl which is unsubstituted or substituted by hydroxyl, sulfo orsulfato and, with the exception of methyl, may be interrupted by oxygen,X₁ is chloro or fluoro, B₁ is methylene-phenylene-methylene which isunsubstituted or substituted in the phenylene ring by C₁-C₄ alkyl, C₁-C₄alkoxy, C₂-C₄ alkanoylamino, halogen, carboxy or sulfo, or is a radicalof formula —CH₂—CH₂—CH(C₂H₅)—, —CH₂—CH(OH)—CH₂— or —CH₂—C(CH₃)₂—CH₂—, Yis hydrogen, or C₁-C₁₂ alkyl which is unsubstituted or substituted byhydroxyl, sulfo or sulfato and, with the exception of methyl, may beinterrupted by oxygen, or phenyl or naphthyl, each unsubstituted orsubstituted by C₁-C₄ alkyl, C₁-C₄ alkoxy, C₂-C₄ alkanoylamino, halogen,carboxy, sulfo or a radical of formula —SO₂-Z, wherein Z is a group offormula —CH═CH₂ or —CH₂—CH₂—U₁, and U₁ is a leaving group, or Y is ananthraquinone of the formula

wherein B₂ is C₂-C₁₂ alkylene which is unsubstituted or substituted byhydroxyl, sulfo or sulfato, and which may be interrupted by oxygen, ormethylene-phenylene-methylene which is unsubstituted or substituted inthe phenylene ring by C₁-C₄ alkyl, C₁-C₄ alkoxy, C₂-C₄ alkanoylamino,halogen, carboxy or sulfo.
 17. An anthraquinone dye according to claim16, wherein R₁ and R₂ are hydrogen or C₁-C₄ alkyl, and R₃ is hydrogen orC₁-C₈ alkyl which is unsubstituted or substituted by hydroxyl, sulfo orsulfato and, with the exception of methyl, may be interrupted by oxygen.18. An anthraquinone dye according to claim 16, wherein R₁, R₂ and R₃are hydrogen.
 19. An anthraquinone dye according to claim 16, wherein Yis phenyl or naphthyl, each unsubstituted or substituted by C₁-C₄ alkyl,C₁-C₄ alkoxy, halogen, sulfo or a radical of formula —SO₂-Z wherein Z isa group of the formula —CH═CH₂ or —CH₂—CH₂—U₁ and U₁ is chloro orsulfato.
 20. An anthraquinone dye according to claim 16, wherein B₁ ismethylene-phenylene-methylene which is unsubstituted or substituted inthe phenylene ring by C₁-C₄ alkyl, C₁-C₄ alkoxy, C₂-C₄ alkanoylamino,halogen, carboxy or sulfo, or is a radical of formula —CH₂—C(CH₃)₂—CH₂—.21. An anthraquinone dye according to claim 20, wherein B₁ ismethylene-phenylene-methylene or a radical of formula —CH₂—C(CH₃)₂—CH₂—.22. An anthraquinone dye according to claim 21, wherein B₁ is a radicalof formula —CH₂—C(CH₃)₂—CH₂—.
 23. An anthraquinone dye according toclaim 16, of formula

wherein R₆, R₇ and R₈ are each independently of one another hydrogen,C₁-C₄ alkyl, C₁-C₄ alkoxy, halogen, sulfo or a radical of formula—SO₂-Z, wherein Z is a group of formula —CH═CH₂ or —CH₂—CH₂—U₁, and U₁is chloro or sulfato.
 24. An anthraquinone dye of formula (5) accordingto claim 23, wherein R₆, R₇ and R₈ are each independently of one anotherhydrogen or sulfo.
 25. An anthraquinone dye according to claim 23,wherein the dye of formula (5) is a dye of formula


26. A method of dyeing or printing a hydroxyl-group-containing ornitrogen-containing fibre material, which comprises the step of applyingto said fibre material a tinctorially effective amount of ananthraquinone dye according to claim
 16. 27. A method according to claim26 wherein the fibre material is a cellulosic fibre material or anatural or synthetic polyamide fibre material.